JPH02187463A - Preparation of aqueous emulsion of high-molecular weight organopolysiloxane which is solid at room temperature - Google Patents

Abstract

Process for the preparation of aqueous emulsions of high-molecular weight organopolysiloxanes which are solid at room temperature, without the use of organic solvents by dissolving the high-molecular weight organopolysiloxane which is solid at room temperature in a low- molecular weight organo(poly)siloxane which is liquid at room temperature, and emulsifying this solution with water after addition of an emulsifier and, if desired, conventional additives.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Corporation] The invention relates to a process VC for producing aqueous emulsions of high molecular weight organopolysiloxanes that are solid at room temperature without the use of bulking agents.

[Conventional technology]

Environmental protection measures include avoiding the use of alkaline bath additives in chemical compositions. The use of water-based threads makes it even more appealing. Organic solvents are not suitable for use in axes due to their cumbersome properties and the risk of soot burning.

The preparation of aqueous emulsions of organopolysiloxanes is known per se in many ways. European Special Liver Detail Publication No. 157 32
No. 3 Specification 1 (Published on October 9, 1985 -, w, ()
Bayer AG) S U.S. Patent No. 4
Specification No. 582 874 (Date of issue: April 15, 1986)
JP, W. Grape et al., Bayer G), UK Revised Patent No. 2 085 903 (issued June 1985).
Month 19, 1', Travel %General
1lectrio Co,) and US Patent #! 4 5
52 No. 910 (issue date November 12, 1985, B. Dsubsser et al., Wacker-Oh.mi.
Aqueous emulsions of organopolysiloxanes are described in GmbH, ) in which organopolysiloxanes in liquid state or in solution with organic solvents are added to suitable emulsifiers. It is emulsified in water. However, the preparation of such emulsions encounters difficulties when high molecular weight organopolysiloxanes, which often occur in crystalline or at least glassy form, are to be emulsified in water without the aid of organic solvents. In this case, the emulsification step can be carried out using equipment corresponding to the conventional known technology, e.g.
Guinolper (8tativ-Dissolver)
, Turrax, etc. cannot be used. Canadian Patent No. 12 05 937 Specification V (
Publication date June 10, 1986 - F, Traver,
General 1lectrl.

CO,) describes the preparation of aqueous emulsions of organopolysiloxane resins. The emulsification step is carried out by grinding in a colloid mill and the resulting aqueous thread is then printed with organopolysil-kF! It is considered as liquid A and must be added vigorously.

[Problem to be solved by the invention]

It is possible to make storage-stable aqueous emulsions of high molecular weight organopolysiloxanes that are solid at room temperature without the use of organic solvents, and this vA is based on the chemical properties of the individual components or additives as well as their emulsions. 111 problems arise in which we try to provide a method that can be widely changed in the inner school club.

[Means to resolve the issue]

This glandular sprout is manipulated according to the present invention.

The object of the present invention is a method for preparing aqueous emulsions of high molecular weight organopolysiloxanes that are solid at room temperature, which method comprises adding low molecular weight organopolysiloxanes that are solid at room temperature to low molecular weight organopolysiloxanes that are solid at room temperature. ) Dissolved in siloxane and emulsified this solution with water with the addition of an emulsifier and, if necessary, customary additives.

As a high molecular weight organopolysiloxane that is solid at room temperature,
The process according to the invention is preferably carried out by the general formula [wherein R represents the same or different monovalent hydrocarbon radicals having from 1 to 14 carbon atoms in each radical, in which this radical is intolerant to water. may have active substituents, R1 may be the same or different, and the scale atoms 17'C represent seven alkyl groups each having from 1 to 4 carbon atoms, and a is o
, i, 217'c are 6, average 0.75 to 1.5, preferably average 0.9 to 1.1, and b is 0.1.2 or 6, average 0.0 to 1.1 Advantageously average 0.01-0.07
), provided that these organopolysiloxanes have a molecular weight of at least 4000 g/mol.

The high molecular weight organopolysiloxane used in the method of the invention is a -sensing high molecular weight organopolysiloxane.

However, mixtures of at least two different classes of such high molecular weight organopolysiloxanes may also be used.

Lateral alkyl groups of the group R, such as methyl, ethyl and propyl groups, alkenyl groups such as vinyl groups, and 7
A lyl group is, for example, a phenyl group.

An example of a substituted hydrocarbon group R is 3.3.3-1>fluoroterovir group.

Preferred radicals R are methyl, 7-enyl and propyl.

Examples of radicals R1 are methyl, ethyl and propyl, ethyl being preferred.

The preparation of the high molecular weight organopolysiloxanes which are solid at room temperature and are used according to the invention is known and is described, for example, in British Patent No. 685 173 (issued 6 December 1951).
1st, DOW OOrning Limited), US 1% Permit m2B 42 521 Specification (Issuance date 195
July 8, 8, 8. N1etsche et al., Wacker
-Chemie GmbH), France % Total No. 14 7
5 Specification No. 709 (Publication date: April 7, 1967, Ge
neral Electric Company),
U.S. Pat. No. 36,68,180 (issue date: 197
June 6, 2016, J, L, Brennen$, 8 tauf
fer-Walker-8111cone Corpo
ration, etc.), Thu @ Patent No. 37 92 071 specification! (Date of publication February 12, 1974 Ss, N1etsc
Wacker-Ohemie GmbH et al.), U.S. Pat.

General Electric Company
) and Wood 1% Total Specification No. 42 98 753 (Publication date: November 3, 1981, A, 5 China'beck
4, Wacker-Chemie GmbH).

Preference is given to the formula 0H31310 (OCI2Ha) as high molecular weight organopolysiloxane in the process according to the invention. ,. 61
・9? and a molecular weight of at least 4000F1 mol is used.

The low/molecular weight organo(poly)siloxanes used according to the invention preferably have the general formula %, in which R2 is the same or different monovalent carbide having from 1 to 14 carbon atoms for each group. hydrogen radicals, in which this group may have substituents which are inert towards water, R3 may be the same or different and have a hydrogen atom or each radical has from 1 to 4 carbon atoms; Represents an alkyl group, and C is 0.1.2! or 6, average 0.0-6.
9, preferably on average 0.9 to 1.1 υ and d 0.1
．． 219 is 6, average 0.2-6.9, preferably average 0.8
~1.5] (in this case, their organo (borine siloxane per molecule per molecule) sl-
having 1 to 20 atoms and 0.5 to 1 at 25°C
Viscosity of 00 mPa, s, preferably 2 to 2 Q mPa,
(with the condition that it represents the viscosity of s).

Examples of radicals R10 are alkyl radicals, such as methyl and ethyl, the methyl radical being preferred.

An example of a substituted hydrocarbon group R2+ is a 3,5,3-trifluoropropyl group.

Examples of radicals R3 are methyl and ethyl, the ethyl radical being preferred.

The low molecular weight organosiloxanes used according to the invention can be prepared in the same manner as the high molecular weight organopolysiloxanes described above.

Advantageously, in the uninvented method, the formula (jH3BiO(QC2B5
A low molecular weight organo(poly)siloxane having a viscosity of 20 mPa, e at 25° C. of 9.81·1 was used.

The aqueous emulsion of organopolysiloxane on sieve molecules produced by the method of the present invention contains low molecular weight organopolysiloxane (
Poly)siloxane gold preferably 1 to 200% by weight, in particular 20% by weight
It is contained in an amount of ~50% by weight, particularly preferably 35-45]1[Ji%.

In this method, all ionic emulsifiers and nonionic emulsifiers conventionally well known as emulsifiers can be used alone or in mixtures of various emulsifiers (conventionally, stable aqueous emulsions of organopolysiloxanes can be prepared). )
Available for use. For example, West Germany Patent No. 361338
Specification No. 4 or corresponding U.S. citizenship permit 934 U, J
8. N.

It is also possible to use the emulsifiers described in US Pat. No. 19,988. Preference is given to using nonionic emulsifiers. Particular preference is given here to using emulsifiers based on polyethylene glyco-yl, such as intridecyl alcohol polyethylene oxide ether, which has an average of 16 cyto units in the edelenol.

The aqueous emulsions of high molecular weight organosiloxanes produced by the process of the invention each contain an emulsifier of 0.1 to 0.1 to the excess of the high molecular weight organopolysiloxane and low molecular weight organosiloxane used. Contains 1% in 503.

The aqueous emulsion of a high molecular weight organopolysiloxane that is solid at foot temperature according to the present invention is prepared by bathing in a low molecular weight organo(poly)siloxane of a high molecular weight organopolysiloxane wxi liquid that is solid at foot temperature, and Turn the solution into an emulsifier with water! It is manufactured by emulsifying while adding. Depending on its chemical nature, the emulsifier can be present both in the aqueous phase and in the oil phase. The dissolution of the high molecular weight organopolysiloxane in the low molecular weight organo(poly)siloxane, e.g. the emulsification step, can be carried out using a conventional mixer suitable for the production of emulsions, e.g.
It may be carried out in a high speed stationary-rotating stirrer according to F., P. Wi'llems. After the emulsification step, the emulsion/powder is diluted with water in the desired manner.

The aqueous emulsions of nine high molecular weight organopolysiloxanes produced by the process of the invention preferably contain from 1 to 80% by weight of solid gold 1, in particular from 60 to 60% by weight, in each case based on the total emulsion. :i%
, particularly preferably from 45 to 551% by weight.

In addition, if appropriate, the catalyst may also be supplemented with customary additives, preferably selected from the group of metal salts, thixotropic agents, pigments, acids or bases and preservatives. The amount of addition depends on the respective intended use of the emulsion and the required properties.

The method of adding additives can vary and depend on their chemical nature. Thus, for example, water-soluble substances can be added to the aqueous phase and water-insoluble substances to the oil phase. In particular, the additives may be added to the emulsion already produced, the additives having to not degrade on the emulsion produced.

As is known to those skilled in the art, even though aqueous emulsions of low molecular weight organo(poly)siloxanes exhibit significantly low storage stability, i.e. tend to settle within a few days, they can still be processed by the process of the invention. The emulsion of high-molecular weight organopolysiloxane, which remains solid at foot temperature, exhibits extremely high storage stability for a longer period of time than at foot temperature.

The process according to the invention provides an advantage in the preparation of any solvent-free emulsions of solid, high molecular weight organopolysiloxanes at home temperature which can be used for C purposes, especially when no organic solvents should be present. do.

Such aqueous emulsions can be used, for example, as binders for water-based paints, as laxatives on inorganic supports, as additives for organic dispersions, as hydrophobic agents and binders in textile materials, etc. However, in this case, it is possible or necessary to add various additives depending on the purpose of use.

〔Example〕

The invention will be explained in more detail with reference to the following examples, "Zheng" and "%
” All descriptions are in writing, unless otherwise specified.
It is against.

All of the following abbreviations are used in chemical formulas: Me: -0H3 11it: -02"5 Example 1 Summative formula Me810 (Oit) (Siloxane) 1 fist 48 Organopolysiloxane (Wacker) solid at room temperature of 0.04
-Ohemie GmbH (Mixnchen) (Purchased under the trade name "@FestharzMK") 70
Part t1 summation formula Me810 (ozt). , 8 (siloxane B) has a viscosity of 25 mPa, a at 25°C (Waoker-Ohe
Product name of mie GmbH (located in Miincben) @
30 parts (purchased at Traail') are dissolved by ultrasound-irradiation. The resulting mixture has a viscosity of approximately 180 Pa, B at 25°C.

To this organopolysiloxane solution 1150 II, Griinau (11lertiase)
Polyethylene glycol (isotridecyl alcohol having an average of 16 polyethylene oxyl units) available under the trade name "Ar17pOn Engineering T 16" manufactured by
Add nonionic emulsifier 9II based on polyethylene oxide ether) 1 and stir. This mixture is then transferred to an emulsifying device such as "t71tra-Turr!"
Emulsify by adding 141 g of deionized water with constant stirring at LX''.
An aqueous emulsion of a high molecular weight organopolysiloxane with a solids content of k% is obtained.

The produced emulsion was centrifuged at M (rotation speed = 40001).
, m1n-1) does not show any sedimentation phenomenon even after 11-i hours. This emulsion is stable for longer periods than six months at room temperature.

EXAMPLE 2 The procedure described in Example 1 was replaced with the emulsifier used by Waaher-Ohemie GmbH.
bH, Munahen) product name @PO17ViO
A 10% aqueous solution of IW25/140"O&!7 vinyl alcohol is used and emulsified with deionized water 909. Aqueous high molecular weight organopolysiloxane with 52 wt-i% solid gold*r based on the total emulsion. An emulsion is obtained.

The produced emulsion is centrifuged for 1s (Ii;!J rotation number:
4000U, rnin-')'1 No sedimentation phenomenon was observed even after 1 hour of testing. This emulsion is stable for longer periods than six months at room temperature.

Example 3 The procedure described in Example 1 is repeated, but with the addition of a high molecular weight organopolysiloxane (Siloxane A) that is solid at room temperature and an organo(poly)siloxane (Siloxane 7B) that is liquid at room temperature.
) Used at a k-weight ffi ratio of 1:1. An aqueous emulsion of a high molecular weight organopolysiloxane having 521 i% of solid gold ikt, based on the total emulsion, is obtained.

The produced emulsion was centrifuged (rotation speed: 4000 U).
omin-1) k 1 It does not show a sinking nm phenomenon even if the time increases. This emulsion is stable for longer periods than six months at room temperature.

Example 4 An ionic emulsifier prepared as follows is used as emulsifier: 4 g of methanol (4 g) with stirring in a three-hole flask (A) of fcIJ equipped with a stirrer, a dropping funnel and a reflux condenser.
oHO, 2 & 500 g of Siloxane B as described in Example 1
N-(2-aminoether)-6-7
Minozolovirtrimethoxysilane (Waaker-Ch
emie Gmt+H.

(y, 1inohen E) 'L product name of Jh' E3
11an GIF 91") is added. The mixture is refluxed for 26 hours and then heated to a boiling point of 1.5°C, then cooled to 30°C and diluted with 10% hydrochloric acid in water.
No. 59 is mixed, heated to 140° C. to remove the four components, and filtered. Shiro medium t15 obtained in this way
3.3.9' mix wood vinegar i16.7 g f'j-, b.

The siloxane/glacial acetic acid mixture 4 S gies has a viscosity of approximately 180 I'a, s'' at 25°C as described in Example 1.
'r: Add to 105 g of a certain siloxane mixture. Next, add this mixture to the procedure described in Section 1 above and add deionized water. Float with i. 49 weight I% based on the total amount of emulsion
An aqueous emulsion of a high molecular weight organopolysiloxane is obtained having a solids content of .

The back-channeled emulsion is centrifuged (rotation speed: 4000 U).
, m1n-1) 'k No sedimentation phenomenon was observed even after 1 hour of testing. It is stable for a longer period of time than six months at room temperature.

Example 5 The procedure described in Example 4 is repeated, but the procedure described in Example 1 is
Siloxane with a viscosity of 0 Pa, s
70 parts of a high molecular weight organopolysiloxane (siloxane A) solid at room temperature of
(OMe) o, e (Siloxa 7CJ) (Wao
It is dissolved in 760 parts of organo(poly)siloxa from Ker-Ohemie GmbH, Mtlnahsn, available under the trade name "VP 2265" from HA. An aqueous emulsion of a high molecular weight organopolysiloxane is obtained which contains 50% solid gold based on the total weight of the emulsion.

The produced emulsion was centrifuged (11 g 1 turnover = 400
0 U, win"") 'c No sedimentation phenomenon is shown even after 1 hour. This emulsion is stable for a long period of time at layer temperature.

Example 6 The procedure described in Example 1 is repeated, but the summation formula s1o is substituted for the nine organo(poly)siloxanes used in Example 1.
(oElt) (Siloxane D) 0Φ815
2.5 Organo(
Poly)siloxane (Wacker-Chemia Gm
Product name manufactured by bH (based in Minchen) 81:Li
kat TEEI 4Q') is used. An aqueous emulsion of a high molecular weight organopolysiloxane is obtained having a solids content of 51% by weight, based on the total weight of the emulsion.

Artificial milk/lie fluid is centrifuged! 1lI (number of revolutions:
4000 U0 min''''1) Even after 1 hour, sedimentation phenomenon was observed. This is stable for a longer period of time than June at layer temperature.

Example 7 70 parts of organopolysiloxane (siloxane A) solid at room temperature as described in Example 1 k, a Japanese formula Me81 (OEt) 3
(Silane E) with a viscosity of Q, 6 mPa, s at 25°C (Wacker-Ohemie Gmb
H (at Munohen) fA product name @811an-M
1-Dissolve in 30 parts (obtained from Triethoxy'). For dissolution, a first wave of ultrasonic irradiation can be used in this case with a suitable mixer.

1 polyvinyl alcohol (Waoker-Chemie Gmb
Product name: “PO17ViOI” manufactured by H (Munahen)
Disperse seven 10% aqueous solutions of W 25/140'').

This mixture t is then passed through an emulsifier, for example an "Ultra-T"
Emulsify by adding 90 g of deionized water with constant stirring at ``urrax''.
An aqueous emulsion of a molecular weight organopolysiloxane having 1% of solid gold is obtained.

The produced emulsion was centrifuged (rotation speed: 4000 U).
, min"-1) k, even after 1 hour of no sedimentation phenomenon. This emulsion is stable for longer than 6 months at layer temperature.

Claims (1)

[Claims] 1. A method for producing an aqueous emulsion of a high molecular weight organopolysiloxane that is solid at room temperature, in which a high molecular weight organopolysiloxane that is solid at room temperature is mixed in a low molecular weight organo(poly)siloxane that is liquid at room temperature. A process for producing aqueous emulsions of high molecular weight organopolysiloxanes which are solid at room temperature and which is characterized in that this solution is emulsified with water with the addition of emulsifiers and optionally customary additives. 2. As a high molecular weight organopolysiloxane, the formula R_a(R^1O)_bSiO_[_4_-_(_a_
+_b_)_]_/_2 [In the formula, R represents the same or different monovalent hydrocarbon radicals having 1 to 14 carbon atoms for each radical, in which the radicals are water-inert. R^1 may have a substituent, and R^1 may be the same or different, and each group represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a is 0, 1
, 2 or 3, average 0.75-1.5 and b is 0
, 1, 2 or 3, on average from 0.0 to 1.1], provided that these organopolysiloxanes have a molecular weight of at least 4000 g/mol. The method described in 1. 3. As a low molecular weight organo(poly)siloxane, the formula R^2_c(R^3O)_dSiO_[_4_-_(_
c_+_d_)_]_/_2 [wherein R^2 represents the same or different monovalent hydrocarbon radicals having from 1 to 14 carbon atoms for each radical, in which the radicals are indifferent to water. may have active substituents, R^3 may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms for each group, c is 0
, 1, 2 or 3, average 0.0-3.9, and d
is 0, 1, 2 or 3, with an average of 0.2 to 3.9].
Poly)siloxane has 1 to 20 Si atoms per molecule.
and 0.5 to 100 mPa at 25°C. 3. The method according to claim 1 or 2, wherein the viscosity is s.